Process of making the arylamids of 2.3-oxynaphthoic acid.



, UNITED STATES PATENT OFFICE.

ARTHUR zrrscnnn, or orrnnnAcn-on-rnn-mam, GERMANY, assronon' THE con ronn'rron or oHEMIscHn FABRIK GRIESHEIMELEKTRON,' or rnanm'onr-on- THE-MAIN, GERMANY.

PRocEss on MAKING THE ARYLAMIDS tr as-oxxnarnrnorc Ann);

No Drawing.

Specification of Letters rat ant. Patented J 111923, 1914, Application filed November 14, 1918.1 'fseiiaino. 300,951.

To all whom it may concern:

,Be it known that I, ARTHUR Zrrsonnn, doctor of philosophy, chemist, citizen of the German Empire and resident of Offenbachon-the-Main, in the Grand Duchy of Hesse,

Germany, with the post-otfice address Freidrichstrasse 31, have invented new and use ful Improvements in the Process of Making the Arylamids of 2.3-Oxynaphthoic Acid, of which the following is a specification.

My invention relates to a process of mak: ing arylarnids of 2:3-oxynaphthoic acid consisting in heating 2:3-oxynaphthoic acid and an arylamin with a dehydrating agent in an indifferent diluent.

"dichloro-anilins or diami ns resinous, very darkly colored by-products are formed, and by condensing the said acid with naphthy1- amins dinaphtylamins are also obtained in a considerable quantity (see Strohbach, Berichte dcr Deutschcn Ghemz'schen Gesellschaft 34:, page 4152). These by-products must be removed by a troublesome purification to bring the product into a form adapted for the production of dyestufis. For that reason the yield of pure product is but small. Compared with this process the present invention is .very advantageous owing to its excellent yield and the purity of the arylamids of 2:3-oxynaphthoic acid obtained. 7

According to the present process it is easy to condense 2:3-oxynaphthoi-c acid with anilin itself, its homologues and chlorosubstitution products with anisidins, chlorotoluidins and chloro-anisidins, with amino phenols, with diamino-bases, for example with para-phenylenediamin, meta-phenylene-diamin and the bases belonging to the diphenyl series such as benzidin and tolidin and also with naphtylamins and so on. All thesefa-rylamids of 2:3-oxynaphthoic acid As dehydrating. jagents can be employed for instance phos are-important intermediate products'jor the production of azo-dyestufis.

The-following examples illustrate the invention, the parts being by weighti V Examp 188 parts of 2;3.'- ay thoic acid are suspended in toluene, 93 parts of anilin are added while stirringand 60 partsof phosphorus trichlorid are dropped into the mixture. The mass is ILQW'bOilBd under the reflux condenser, while continuously stirring, until no free amin can be detected, then sodium carbonate is added until the reaction is alkaline, and the toluene is expelled by steam. The residue is filtered, well washed and dried. The anilid of 2:3- oxynaphthoic acid, thus obtained, "forms a colorless powder directly melting at 243' Example II: 188 parts of finely ground 2:3-oxynaphthoic acid and 140 parts of finely ground 2-naphthylamin are suspended in xylene, and at (SO-70 70 parts of'phosphorus trichlorid are dropped in. The mixture is heated to 110-120 while well stirring, until the reaction" is complete. After working up, as described above, the Q-naphthalid of 2:3-oxynaphthoic acid is obtained as an almost colorless powder melting at 241-242", when crystallized from chlorobenzene, the compound forms lustrous needles melting at 243244.

Example III: A mixture of 188 parts of I 2:3-oxynaphthoic acid and 154 arts of 2:5 dichloroanilin in xylene is mixed with 150 parts of thionyl chlorid and the mixture is heated while stirring at 110120 until the reaction is complete. Then the mixture is mixed with sodium carbonate until the reaction is alkaline, the xylene is expelled by steam, the residue is filtered While hot,-well washed and dried. The 2:5-dichloroanilid of 2:3-0Xynaphthoic acid, thus obtained, forms, when crystallized from alcohol, slender lustrous needles melting at 246247.

, Example IV: Into a suspension of 188 parts of 2:3-oxynaphthoic acid and 55 parts of 2:4-toluylenediamin in toluene, heated to 7 0, 70 parts of phosphorus-trichlorid are slowly dropped. The mixture is boiled in a reflux apparatus until the reaction is complete. Then the mixture is mixed with sodium carbonate until the reaction is alkaline, and the toluene is expelled by steam. The residue is filtered, while hot, well washed and dried. The condensation product, thus from acetic acid, it forms slender rods melt- 10 obtained, of the formula; in at 26l262.

n enalogous manner the diamins belong- W m1 zm in to the diphenyl series can be conde 5 with two or also only with one molecular k k/k l pralwporltionf (if 2:3-onyxgphtfiwic ecid. f 15 n he 0 owing ta e t e properties 0 EH HO some of the arylamids obtainable according forms :1 colorless powder. Crysfialllzed to the present process are described:

V Melting Color of t he Arylnmiile of mommphmle W61. 0mm lzcmpoflint. Aspect. diluted mastic Lanccolated leafims Yellow. Colorless matted needles. Yellow. Colorless needles: Colorless leaflets Almost colorless cr stamne Wd Fine lustrous ne es, Golorless leaflets Colmleas needles. Yellow.

' solvem'aiil'niif Solvent magehtha,

a phimud (a em X lenewizfaun. wt colorgsess gf eggg. 2L mam! n... 1 1 e (15111 1111 12 gvith 2z4-t0lnyl9nediamin (Ex- Mellow: slend r les Yellow.

mnp fifiio x flfinitxx::::::::::::;:::::: gfillfifilfiflilfiilll llfil ;fi%ly3?nsa;6sae::::::::::: llfillt.

Wm deoemponladen. V N ow what I claim and desire to secure by as my invention, have signed my name in no Letters Patent 1s the fpllowmg: presence of two wmnesscs, llhlS thlmeth day The process of mak1ng arylamids of 2 23 of October 1913. oxynaphthoic 101d consisting in heating Z R 2:3-oxynapl1tho1c acid end miner 13min with ARTHUR ITEBCHE a, delaydreung agent m an m ifi'ereni; di- WHnessesi '25 luent. Perm LAUTENSCHLKGEB,

In testimony, that I 01mm the foregoing BUDOLE KIMPEL, 

